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Living radical polymerization method using alcohol as catalyst

Foreign code F120006114
File No. S2008-0177
Posted date Jan 6, 2012
Country United States of America
Application number 99183809
Gazette No. 20110124832
Gazette No. 8378044
Date of filing Feb 6, 2009
Gazette Date May 26, 2011
Gazette Date Feb 19, 2013
International application number JP2009052115
International publication number WO2009136510
Date of international filing Feb 6, 2009
Date of international publication Nov 12, 2009
Priority data
  • P2008-123817 (May 9, 2008) JP
  • 2009WO-JP52115 (Feb 6, 2009) WO
Title Living radical polymerization method using alcohol as catalyst
Abstract (US8378044)
Provided is a low-cost, environmentally friendly living radical polymerization catalyst having high activity.
The catalyst is used for a living radical polymerization method, and contains a central element consisting of oxygen and at least one halogen atom bound to the central element.
Furthermore, an alcohol compound can be used as a catalyst precursor.
By polymerizing a monomer in the presence of the catalyst, a polymer having narrow molecular weight distribution can be obtained, and the cost of the living radical polymerization can be remarkably reduced.
The present invention is significantly more environmentally friendly and economically excellent than conventional living radical polymerization methods, due to advantages of the catalyst such as low toxicity of the catalyst, low amount of the catalyst necessary, high solubility of the catalyst, mild reaction conditions, and no coloration/no odor (which do not require a post-treatment for a molded article), and the like.
Scope of claims [claim1]
1. A method of conducting a living radical polymerization, comprising: reacting a radical generated from a radical initiator and a catalyst precursor compound to form an activated radical; and
polymerizing a monomer having a radical reactive unsaturated bond using the activated radical to obtain a polymer;
wherein the precursor compound comprises at least one hydroxyl group bonded to carbon, silicon, nitrogen, or phosphorus,
a radical generated from the radical initiator abstracts a hydrogen atom from the hydroxyl group in the precursor compound to form the activated radical, and
the activated radical acts as a living radical catalyst of the polymerization reaction of the monomer,
wherein an organic halide having a carbon-halogen bond is used in the living radical polymerization reaction, and a halogen given from the organic halide is used as a protecting group of a growing chain.
[claim2]
2. The method according to claim 1, wherein an atom bonded to the hydroxyl group is carbon.
[claim3]
3. The method according to claim 1, wherein the atom bonded to the hydroxyl group has a double bond or triple bond between the atom and an adjacent atom, and an activated radical formed after the hydrogen of the hydroxyl group is abstracted is stabilized by the resonance between the radical and the double bond or triple bond.
[claim4]
4. The method according to claim 1, wherein the catalyst precursor compound is alcohol or phenol represented by the formula (I):
R1n(OH)m (I)
wherein R1 is substituted or unsubstituted alkyl, alkenyl, or alkynyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;
n is a positive integer;
m is a positive integer;
wherein the substituent is alkyl, alkenyl, alkylcarboxyl, haloalkyl, alkylcarbonyl, amino, cyano, alkoxy, aryl, or alkyl-substituted aryl;
a carbon chain in R1 has a chain structure or cyclic structure; and
when R1 has a cyclic structure, the cyclic structure may be a fused cyclic structure in which one or more rings are fused to an aryl or heteroaryl ring, wherein one or more cyclic structures fused to the aryl or heteroaryl ring may be a heterocycle containing an oxygen or nitrogen atom as a heteroatom.
[claim5]
5. A catalyst for a living radical polymerization method, which consists of a compound comprising: at least one central element which is oxygen; a halogen atom bonded to the central element; and a carbon atom, silicon atom, nitrogen atom or phosphorus atom bonded to the central element.
[claim6]
6. The catalyst according to claim 5, wherein the central element is bonded to a halogen atom and a carbon atom.
[claim7]
7. The catalyst according to claim 5, wherein the catalyst has a structure in which an atom bonded to the central element has a double bond or triple bond between the atom and an adjacent atom, and an activated radical formed after the halogen atom bonded to the central element is eliminated is stabilized by the resonance between the radical and the double bond or triple bond.
[claim8]
8. The catalyst according to claim 5, which consists of a compound of the following general formula (Ia):
R1n(OX1)m (Ia)
wherein R1 is alkyl, alkylcarboxyl, haloalkyl, alkylcarbonyl, alkenyl, alkynyl, aryl, heteroaryl, substituted aryl, or substituted heteroaryl,
n is a positive integer;
m is a positive integer;
X1 is halogen.
[claim9]
9. The catalyst according to claim 5, wherein the halogen is iodine or bromine.
[claim10]
10. The catalyst according to claim 5, wherein the halogen is iodine.
[claim11]
11. A polymerization method comprising conducting a living radical polymerization, wherein the living radical polymerization step is conducted in the presence of the catalyst according to claim 5.
[claim12]
12. The method according to claim 1, wherein a concentration of the catalyst in a reaction solution is 0.75 wt % or less.
[claim13]
13. The method according to claim 1, wherein a reaction temperature is 20 to 100 deg. C.
[claim14]
14. The method according to claim 1, wherein two or three carbon atoms are bonded to the carbon atom to which the halogen in the organic halide is bonded.
  • Inventor, and Inventor/Applicant
  • GOTO ATSUSHI
  • FUKUDA TAKESHI
  • TSUJII YOSHINOBU
  • KYOTO UNIVERSITY
IPC(International Patent Classification)
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